Thermally Activated Delayed Fluorescence Research Articles

Excited-state Engineering Enables Efficient Deep-blue Light-emitting Diodes Exhibiting BT.2020 Color Gamut.

Organic luminescent materials that exhibit thermally activated delayed fluorescence (TADF) can convert non-emissive triplet excitons into emissive singlet states through a reverse intersystem crossing (RISC) process. Therefore, they have tremendous potential for applications in organic light-emitting diodes (OLEDs). However, with the development of ultra-high definition 4K/8K display technologies, designing efficient deep-blue TADF materials to achieve the Commission Internationale de l'Éclairage (CIE) coordinates fulfilling BT.2020 remains a significant challenge. Here, we propose an effective approach to design deep-blue TADF molecules based on hybrid long- and short-range charge-transfer by incorporation of multiple donor moieties into organoboron multiple resonance acceptors. The resulting TADF molecule exhibits deep-blue emission at 414nm with a full width at half maximum (FWHM) of 29nm, together with a thousand-fold increase in RISC rate. OLEDs based on our champion material achieved a record maximum external quantum efficiency (EQE) of 22.8% with CIE coordinates of (0.163, 0.046), approaching the coordinates of the BT.2020 blue standard. Moreover, TADF-assisted fluorescence devices employing our designed material as a sensitizer exhibited an exceptional EQE of 33.1%. Our work thus provides a blueprint for future development of efficient deep-blue TADF emitters, representing an important milestone towards meeting the blue color gamut standard of BT.2020. This article is protected by copyright. All rights reserved.

Organic Donor‐Acceptor Thermally Activated Delayed Fluorescence Photocatalysts in the Photoinduced Dehalogenation of Aryl Halides

We report a family of donor‐acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC‐TRZ, that are strongly photoreducing. Both Eox and thus E*ox could be tuned via substitution of the DMAC donor with a Hammett series of p‐substituted phenyl moieties while Ered remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to Ered = ‐2.72 V could be dehalogenated at low PC loading (1 mol%) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.

Role of Bridging Groups in Regulating the Luminescence and Charge Transfer Properties of Thermally Activated Delayed Fluorescence Molecules: A Theoretical Perspective.

Organic emitters with a simultaneous combination of aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) characteristics are in great demand due to their excellent comprehensive performances toward efficient organic light-emitting diodes (OLEDs), biomedical imaging, and the telecommunications field. However, the development of efficient AIE-TADF materials remains a substantial challenge. In this work, light-emitting properties of two AIE-TADF molecules with different bridging groups ICz-BP and ICz-DPS are theoretically investigated in the solid state with the combined quantum mechanics/molecular mechanics (QM/MM) method and the thermal vibration correlation function (TVCF) theory. The research indicates that the C═O bridging bond in ICz-BP is more favorable than the S═O bridging bond in ICz-DPS for enhancing the planarity of the acceptor, increasing conjugation, and thereby elevating the transition dipole moment density. Simultaneously, the stacking pattern of ICz-BP in the solid facilitates a reduction in energy gap between S1 and T1 (ΔEST), achieving rapid reverse intersystem crossing rate (kRISC). Furthermore, compared to toluene, the stacking patterns of ICz-BP and ICz-DPS in the solid effectively suppress the out-of-plane wagging vibration of the acceptor, thereby inhibiting the loss of nonradiative energy in the excited state and realizing aggregation-induced emission. Moreover, the charge transport properties of both electrons and holes in ICz-BP are found to be higher than the corresponding rates in ICz-DPS, attributed to the smaller internal reorganization energy of ICz-BP in the solid state. Additionally, the calculations reveal a more balanced charge transport characteristic in ICz-BP, contributing to efficient exciton recombination and emission and ultimately mitigating efficiency roll-off. Based on these computational results, we aim to unveil the relationship between molecular structure and light-emitting properties, aiding in the design and development of efficient AIE-TADF devices.

Organic Donor-Acceptor Thermally Activated Delayed Fluorescence Photocatalysts in the Photoinduced Dehalogenation of Aryl Halides.

We report a family of donor-acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC-TRZ, that are strongly photoreducing. Both Eox and thus E*ox could be tuned via substitution of the DMAC donor with a Hammett series of p-substituted phenyl moieties while Ered remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to Ered = -2.72 V could be dehalogenated at low PC loading (1 mol%) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.

Spring Lock: Constructing Cluster Emitters with Colorful TADF from Non‐Conjugated Polymaleimide Helical Chains

AbstractNon‐conjugated luminescent polymers have received much attention due to their excellent flexibility, processability, and biocompatibility. However, the single emission color and low solid‐state luminescence efficiency restrict their further development. Herein, by introducing carboxyl‐terminated alkyl chains on the rigid and helical polymaleimide backbone, a series of non‐conjugated luminescent polymers are designed and synthesized. Due to the “spring lock” formed by the synergism of scalable helical main chains and flexible alkyl side chains, these polymers exhibit effective cluster luminescence with thermally activated delayed fluorescence (TADF) property, thereby significantly improving the solid‐state luminescence efficiency with the quantum yield up to 59.6%. The TADF emission wavelengths of the polymer powders can be tuned from 498 to 639 nm through changing reaction solvents, because the conformation of helical chains forming clusters is sensitive to solvent polarity. Interestingly, metal ions can induce the polymers to construct self‐repairing cluster luminescence gels, which show excellent potential applications in ammonia detection and information encryption. This work not only provides an effective design strategy for the colorful cluster luminescence with high‐efficiency TADF, but also further reveals the cluster luminescence mechanism and enlightens the promising applications of cluster luminescent gels.

Stable All‐Fluorescence White Organic Light‐Emitting Diodes with High Efficiency and High CRI

AbstractWhite organic light‐emitting diodes (WOLEDs) have been regarded as the candidates for next‐generation flat‐panel displays and solid‐state lighting due to their low cost. However, it is still challenging to achieve two‐component WOLEDs with high efficiency, high color index (CRI), and long lifetime. Here, high‐performance all‐fluorescence WOLEDs based on a blue fluorescent emitter and an orange thermally activated delayed fluorescent (TADF) emitter are demonstrated. The optimized all‐fluorescence WOLED with two EMLs presents the maximum external quantum efficiency (EQE), current efficiency (CE), and power efficiency (PE) of 23.4%, 40.2 cd A−1, and 33.2 lm W−1, corresponding to a maximum CRI value of 83.1 and Commission Internationale de L'Eclairage (CIE) coordinate of (0.30, 0.31). To further improve the device stability, the all‐fluorescence WOLEDs with three EMLs and tandem structure are constructed, respectively. Under the premise of ensuring efficiency, in going from the two‐EMLs to the three‐EMLs and the tandem structure, the LT50 (time to 50% of the initial luminance) of all‐fluorescence WOLEDs increase from 601 to 714 h and 1622 h at an initial luminance of 1000 cd m−2. These strategies and results present new insight into the design of all‐fluorescence WOLEDs with high efficiency, high CRI, and extended lifetime.

High-efficiency crystalline white organic light-emitting diodes

Crystalline white organic light-emitting diodes (C-WOLEDs) are promising candidates for lighting and display applications. It is urgently necessary, however, to develop energy-saving and high-efficiency C-WOLEDs that have stable and powerful emission to meet commercial demands. Here, we report a crystalline host matrix (CHM) with embedded nanoaggregates (NA) structure for developing high-performance C-WOLEDs by employing a thermally activated delayed fluorescence (TADF) material and orange phosphorescent dopants (Phos.-D). The CHM-TADFNA-D WOLED exhibit a remarkable EQE of 12.8%, which is the highest performance WOLEDs based on crystalline materials. The device has a quick formation of excitons and a well-designed energy transfer process, and possesses a fast ramping of luminance and current density. Compared to recently reported high-performance WOLEDs based on amorphous material route, the C-WOLED achieves a low series-resistance Joule-heat loss ratio and an enhanced photon output, demonstrating its significant potential in developing the next-generation WOLEDs.

Fluorene-carbazole-based hyperbranched polymers with linear red TADF chromophores for high-efficiency white and red electroluminescent devices

Solution-processed polymer light emitting devices (PLEDs) using high-quality thermally activated delayed fluorescence (TADF) polymers as the emitting layers are attractive, however, high-efficiency white-light TADF polymers are very rare because of the complicated radiative transition channels. In this study, a series of hyperbranched TADF conjugated polymers were designed and synthesized which adopted the linear D-A-type TADF emitter of 1,8-naphthalimide-acridine as red chromophores, conjugated poly(fluorene-carbazole) as the blue backbone and triphenylamine as the hyperbranched cores. By adjusting the appropriate feed ratios of monomers, energy transfer process from the blue backbone to the red chromophores could be regulated and HR0.8 film had the highest photoluminescent quantum yield of 24%. Consequently, its doped electroluminescent device showed the cold-white emission with the CIE color coordinates of (0.35, 0.23) and the maximum EQE of 6.82%. By simply raising the concentration of the red chromophore in the polymers, the rapid reverse intersystem crossing (RISC) process and the enlarged energy gap between S1 and T1 were achievable.

Carbon dot-based afterglow composite with tunable room temperature phosphorescence and thermally activated delayed fluorescence and their anti-counterfeiting and encryption application

Carbon dots (CDs) based afterglow materials have attracted much attention owing to their low toxicity, environmental protection, stable luminescence, abundant raw materials, and low cost. However, CD-based afterglow materials with both room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) characteristics are rarely reported, which greatly limits their in-depth application in advanced anti-counterfeiting, intelligent sensing, and other fields. In this paper, Cu, N co-doped CDs (Cu, N-CDs) with dual emission centers were synthesized via a simple solvothermal method by heteroatom doping to enhance the spin–orbit coupling of CDs and regulate the luminescence properties of CDs. Then, boric acid (BA) was used as the matrix to synthesize Cu, N-CDs@BA composites by matrix-assisted method, and the electron transfer enhancement afterglow was realized by the inorganic electronic defects of the matrix. Cu, N-CDs@BA can realize the mutual conversion of TADF and RTP by changing the excitation wavelength or increasing the temperature. At the excitation of 285 nm, the room temperature afterglow of Cu, N-CDs@BA exhibit TADF, and the average afterglow lifetime is 94.21 ms. At the excitation of 365 nm, they exhibit RTP, and the average afterglow lifetime is 347.96 ms. Based on three different emission properties (fluorescence, RTP, and TADF), Cu, N-CDs@BA was applied in anti-counterfeiting and encryption, which shows good application potential.

Effective exciplex host for solution-processed narrowband blue TADF-OLEDs using a 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole analogue with an adamantane substituent

Implementing an exciplex host system in the emitting layer is crucial for achieving highly efficient thermally activated delayed fluorescence (TADF) and phosphorescent organic light-emitting diodes (OLEDs). In this study, we successfully designed and synthesized 3-((3r,5r,7r)-adamantan-1-yl)-9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (AdCz-DBT) and 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (Cz-DBT) as p-type hosts for the exciplex host implementation, and 7-(4-(tert-butyl)phenyl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene (tPDBA) as an n-type host. The AdCz-DBT host incorporates a large and robust adamantane group into Cz-DBT, increasing molecular weight, film-forming properties and thermal stability. Additionally, AdCz-DBT maintains energy levels and photophysical properties similar to those of adamantane-free Cz-DBT. Efficient exciplex emission was observed in the blend film due to well-matched energy levels of the synthesized p- and n-type hosts. The introduction of adamantane into Cz-DBT did not hinder exciplex formation, resulting in a relatively high photoluminescence quantum yield and improved charge balance in the mixed host with tPDBA.Ultimately, the solution-processed blue TADF-OLED with the AdCz-DBT:tPDBA blend host demonstrated a relatively high external quantum efficiency of 8.00% and a long operational lifetime, exhibiting excellent performance compared to devices using the Cz-DBT:tPDBA blend host.

A supramolecular photosensitizer based on triphenylamine and pyrazine with aggregation-induced emission properties for high-efficiency photooxidation reactions

Recently, there has been a great interest in the study of photocatalysts (PCs) and photosensitizers (PSs) in the field of organic photocatalysis. In the present study, a pure organic thermally activated delayed fluorescence (TADF) molecule 4,4′-(12-(pyridin-4-yl)dibenzo[f,h]pyrido[2,3-b]quinoxaline-3,6-diyl)bis(N,N-diphenylaniline) (DPQ-TPA) was designed and synthesized, which not only have excellent TADF property and small energy splitting (ΔEST), but also can self-assembly in water to form cross-linked nanoparticles with exceptional aggregation-induced emission (AIE) characteristics. DPQ-TPA exhibits excellent remarkable selectivity and notably enhances the production capacity of reactive oxygen species (ROS), particularly 1O2, which was employed as a highly effective photocatalyst in the photooxidation reaction of phosphine and hydroazobenzenes under blue light irradiation with high yields up to 94% and 91%, respectively. This work expands the potential application of (donor-acceptor) D-A type AIE-TADF molecules in photocatalytic organic transformations through supramolecular self-assembly.

Acceptor Copolymerized Axially Chiral Conjugated Polymers with TADF Properties for Efficient Circularly Polarized Electroluminescence.

Chiral conjugated polymer has promoted the development of the efficient circularly polarized electroluminescence (CPEL) device, nevertheless, it remains a challenge to develop chiral polymers with high electroluminescence performance. Herein, by the acceptor copolymerization of axially chiral biphenyl emitting skeleton and benzophenone, a pair of axially chiral conjugated polymers namely R-PAC and S-PAC are synthesized. The target polymers exhibit obvious thermally activated delayed fluorescence (TADF) activities with high photoluminescence quantum yieldsof 81%. Moreover, the chiral polymers display significant circularly polarized luminescence features, with luminescence dissymmetry factor (|glum|) of nearly 3 × 10-3. By using the chiral polymers as emitters, the corresponding circularly polarized organic light-emitting diodes (CP-OLEDs) exhibit efficient CPEL signals with electroluminescence dissymmetry factor|gEL| of 3.4 × 10-3 and high maximum external quantum efficiency (EQEmax) of 17.8%. Notably, considering both EQEmax and |gEL| comprehensively, the device performance of R-PAC and S-PAC is the best among all the reported CP-OLEDs with chiral conjugated polymers as emitters. This work provides a facile approach to constructing chiral conjugated TADF polymers and discloses the potential of axially chiral conjugated luminescent skeletons in architecting high-performance CP-OLEDs.

Host-Guest Doping Modulated Afterglow Emission of Fluoroquinolones for Their Separation-Free Detection and Discrimination.

Detection and discrimination of fluoroquinolones (FQs) are crucial for food safety but remain a formidable challenge due to their minor differences in molecular structures and the serious interferences from food matrices. Herein, we propose an afterglow assay for the detection and discrimination of FQs through modulating their room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) properties by a host-guest doping strategy. FQs were doped into the boric acid host, forming boronic anhydride structures and hydrogen bonds, which prompted the RTP and TADF performance of FQs by stabilizing their excited states, preventing triplet exciton quenching, and reducing the energy gap between singlet and triplet states. The FQs can be quantitatively detected through monitoring the afterglow intensity of host-guest systems, as low as 0.25 μg/mL. The differences in the afterglow intensity and emission lifetime allowed accurate discrimination of 11 types of FQs through pattern recognition methods. Aided by the delayed signal detection model of afterglow emission, the background signal and the interferences from food matrices were effectively eliminated, which endow the detection and discrimination of mixed FQs in commercial meat samples, without multiple-step separation processes.

Two-Coordinate Thermally Activated Delayed Fluorescence Coinage Metal Complexes: Molecular Design, Photophysical Characters, and Device Application.

Since the emergence of the first green light emission from a fluorescent thin-film organic light emitting diode (OLED) in the mid-1980s, a global consumer market for OLED displays has flourished over the past few decades. This growth can primarily be attributed to the development of noble metal phosphorescent emitters that facilitated remarkable gains in electrical conversion efficiency, a broadened color gamut, and vibrant image quality for OLED displays. Despite these achievements, the limited abundance of noble metals in the Earth's crust has spurred ongoing efforts to discover cost-effective electroluminescent materials. One particularly promising avenue is the exploration of thermally activated delayed fluorescence (TADF), a mechanism with the potential to fully harness excitons in OLEDs. Recently, investigations have unveiled TADF in a series of two-coordinate coinage metal (Cu, Ag, and Au) complexes. These organometallic TADF materials exhibit distinctive behavior in comparison to their organic counterparts. They offer benefits such as tunable emissive colors, short TADF emission lifetimes, high luminescent quantum yields, and reasonable stability. Impressively, both vacuum-deposited and solution-processed OLEDs incorporating these materials have achieved outstanding performance. This review encompasses various facets on two-coordinate TADF coinage metal complexes, including molecular design, photophysical characterizations, elucidation of structure-property relationships, and OLED applications.

Efficient narrowband organic light-emitting diodes based on B,O embedded multi-resonance emitters containing B-N covalent bonds

Multi-resonance (MR) thermally activated delayed fluorescence (TADF) materials emerge rapidly in recent years, and are expected to be an effective solution for ultra-high-resolution displays. Solving the main issues of low yield and dangerous lithium reagent for synthesis, extending the material diversity and figuring out the structure–activity relationship would all be beneficial to promote their commercialization. Herein, two easy-to-access MR-TADF emitters, BO-N1 and BO-N2, are constructed by integrating B,O-based MR polycyclic aromatic with B-N covalent bonds. The B-N covalent bonds are formed through simple amine-directed borylation with high yield over 90 %, which significantly improves yield, simplifies procedure and effectively avoids hazardous lithiation compared to the traditional methods. Two emitters exhibit bright green emissions in doped films with full width at half maximum (FWHM) of 28 and 24 nm, and high photoluminescence quantum yields (PLQY) of 85 % and 90 %. The green electroluminescent device of BO-N2 achieves narrow-band spectrum with FWHM of 29 nm, maximum brightness of 10480 cd m−2 and external quantum efficiency (EQE) of 20.1 %.

A figure of merit for efficiency roll-off in TADF-based organic LEDs

Organic light-emitting diodes (OLEDs) are a revolutionary light-emitting display technology that has been successfully commercialized in mobile phones and televisions1,2. The injected charges form both singlet and triplet excitons, and for high efficiency it is important to enable triplets as well as singlets to emit light. At present, materials that harvest triplets by thermally activated delayed fluorescence (TADF) are a very active field of research as an alternative to phosphorescent emitters that usually use heavy metal atoms3,4. Although excellent progress has been made, in most TADF OLEDs there is a severe decrease of efficiency as the drive current is increased, known as efficiency roll-off. So far, much of the literature suggests that efficiency roll-off should be reduced by minimizing the energy difference between singlet and triplet excited states (ΔEST) to maximize the rate of conversion of triplets to singlets by means of reverse intersystem crossing (kRISC)5–20. We analyse the efficiency roll-off in a wide range of TADF OLEDs and find that neither of these parameters fully accounts for the reported efficiency roll-off. By considering the dynamic equilibrium between singlets and triplets in TADF materials, we propose a figure of merit for materials design to reduce efficiency roll-off and discuss its correlation with reported data of TADF OLEDs. Our new figure of merit will guide the design and development of TADF materials that can reduce efficiency roll-off. It will help improve the efficiency of TADF OLEDs at realistic display operating conditions and expand the use of TADF materials to applications that require high brightness, such as lighting, augmented reality and lasing.

Rational Molecular Design via Cyanobenzene Integration for Constructing Efficient Yellow‐Orange Thermally Activated Delayed Fluorescence Emitters

AbstractDeveloping efficient long‐wavelength thermally activated delayed fluorescence (TADF) emitters is a challenging issue due to inherent limitations of the energy‐gap law. In this contribution, a new molecular design of cyanobenzene‐decorated quinoxaline acceptor, combining two or four cyanobenzene acceptors and a rigid carbazole donor, is successfully utilized to construct long‐wavelength TADF emitters (tCzQx2CN and tCzQx4CN). The two additional cyanobenzene units at the 5‐ and 8‐positions of the quinoxaline acceptor are presumed to interlock the molecular rotations and improve the acceptor strength. Compared with tCzQx2CN, tCzQx4CN exhibits orange‐red emission with a considerable bathochromic shift (>35 nm), as expected. Owing to its enhanced charge transfer and well‐separated highest‐occupied and lowest‐unoccupied molecular orbitals, tCzQx4CN exhibits reduced singlet‐triplet energy splitting and improves reverse intersystem crossing. An organic light–emitting diode (OLED) of tCzQx4CN manifestes bright orange‐red emission (λEL ≈581 nm), a superior external quantum efficiency (EQE) of ≈23.7% (compared with that of tCzQx2CN), and a satisfactory operational lifetime. Furthermore, a tCzQx4CN‐sensitized red‐hyperfluorescent OLED device exhibits excellent performance with an EQE of 16.0% and a CIE(x,y) of (0.62, 0.37). This design would potentially pave the way for constructing red/deep‐red TADF emitters by using a diverse combination of donor/acceptor units.

Thermally Activated Delayed Fluorescent Ag(I) Complexes for Highly Efficient Scintillation and High‐Resolution X‐Ray Imaging

AbstractOrganic thermally activated delayed fluorescent (TADF) scintillators hold promising potential for applications in medical radiography and security detection, but the poor X‐ray absorption ability and inferior radioluminescence (RL) hampered their progression. Herein, the study has pioneered the development of high‐performance TADF Ag(I)‐based scintillators from M2X2(dppb)2 (M = Ag, Cu; X = Cl, Br, I) complexes with 1,2‐Bis(diphenylphosphino)benzene (dppb) ligand. In comparison with Cu(I) complexes, the Ag(I) series generally exhibited superior scintillation performance. Notably, Ag2Cl2(dppb)2 (Ag1) stands out with exceptionally high RL intensity (≈125% higher than that of CsI:Tl) and a low detection limit of 59.8 nGy s−1. The outstanding scintillation performance of Ag1 is primarily attributed to the synergistic effect of the high exciton utilization efficiency origin from a small singlet‐triplet energy gap, enhanced X‐ray absorption capacity by heavy atoms, and the high photoluminescence quantum yield (76.47% in ambient atmosphere). By fabricating a flexible film constructed with Ag1 submicron crystalline powders, a high spatial resolution of 25.0 lp mm−1 for X‐ray imaging is obtained. It offers new opportunities for utilizing TADF metal–organic complexes for highly efficient X‐ray scintillation and imaging.

Ultrafast spin-flip exciton conversion and narrowband sky-blue luminescence in a fused polycyclic selenaborin emitter.

Thermally activated delayed fluorescence (TADF) materials with high photoluminescence quantum yields and fast reverse intersystem crossing (RISC) capabilities are highly desirable for applications in high-efficiency organic light-emitting diodes. Herein, we report the synthesis as well as structural and photophysical properties of 5,9-diselena-13b-boranaphtho[3,2,1-de]anthracene (SeBSe) as a narrowband-emissive TADF material. The incorporation of two selenium atoms into the boron-fused pentacyclic π-core results in a small singlet-triplet energy gap (ΔE ST) and thereby significant TADF properties. Moreover, theoretical calculations revealed a noticeable spin-orbit coupling enhancement between the singlet and triplet manifolds in SeBSe by virtue of the heavy-atom effect of selenium atoms. Consequently, SeBSe allows ultrafast spin-flip RISC with the rate constant surpassing 108 s-1, which far exceeds the corresponding fluorescence radiative decay rate (∼106 s-1), enabling an ideal singlet-triplet superimposed excited state.

Coordination of Thermally Activated Delayed Fluorescent Molecules for Efficient and Stable Perovskite Light‐Emitting Diodes

AbstractThe bandgap and operation stability of metal halide perovskites (MHPs) based light‐emitting diodes (PeLEDs) have been compromised by the substantial surface defect densities in the matrix. Today's defect passivation strategies rely on coordination actions of small‐molecular and/or polymeric ligands, which effectively enhance the optical properties of materials. However, the non‐trivial insulating characteristics of the molecules concurrently sacrifice the operation stability and external quantum efficiency (EQE) of the PeLEDs by augmenting the charge injection barrier at the interface. Herein, a coordinative, charge‐polarized organic semiconductor exhibiting thermally activated delayed fluorescence (TADF), namely 9,9‐dimethyl‐10‐(4‐(phenyl sulfonyl)phenyl)‐9,10‐dihydroacridine (SO‐DMAc) is coordinated, into the MHPs matrix for deep‐red PeLEDs. Owing to the distinctive charge transfer (CT) between the molecule and MHPs with exclusive coordination at the MHP's bottom, SO‐DMAc serves as a molecular bridge that significantly augments the hole injection into the PeLEDs. Encouraged by these improvements, efficient and stable deep red PeLEDs offering EQE of 21.8% and respective half lifetimes (T50) of luminance and EQE exceeding 6 and 35 h are demonstrated. It is revealed that the molecular coordination to the MHP surface is pivotal to manifesting the interfacial CT process for favorable energy level tuning.